Aqueous water repellent dispersions comprising a methylene dialkylamide, a methylol cndensate, and a non-ionic surface active agent



3,067,159 AQUEOU WATER REPELLENT DHSPERSEONS COMPRISING A METHYLENE DIALKYL- AMIDE, A METHYLQL CUNDENSATE, AND A NON-lifiiflfi SURFACE ACTIVE AGENT David M. Musser, Fairlawn, N.J., assignor, by rnesne assignments, to Chicopee Manufacturing Corporation, New Brunswick, N.J., a corporation of Massachusetts No Drawing. Filed Oct. 17, 1957, Ser. No. 6%,625 1t) Ciaims. (Ci. 26--29.4)

This invention relates to an improvement in durable water repellent finishes for textile fibers and fabrics.

In the durable water repellent finishes for textile fibers and fabrics used up to the present time the Water repellent substance has consisted of a relatively long chain saturated aliphatic compound having 16 to 30 carbon atoms in the aliphatic chain, such as stearic acid, oleic acid, montanic acid, or the like, chemically combined with a coupling radical in the native quaternary ammonium compound, such as pyridinium chloride. An example of such a compound which is widely used in the production of water repellent cotton cloth is stearamidomethylpyridinium chloride. When applied in solution to a textile fiber or fabric to be rendered water repellent, and heated, the quaternary ammonium compound breaks down, causing a reaction with the cellulose of the fiber and afiixing the long chain fatty radical more or less permanently to the textile fibers by a chemical linkage which has been variously termed an ether and an acetal linkage and imparting a degree of durable water repellency thereto.

These prior art Water repellent compositions are not entirely satisfactory as most of them lose a great percentage of their water repellency ratings after four or five washings or even a lesser number of dry cleanings. They are also difficult to control and apply and unpleasant to work with. The destruction of the quaternary ammonium radical under the heat used to aifix the water repellent composition to the fabric produces degradation products which must be removed from the fabric by further washings. The odor of pyridine coming from the drying ovens and wash tanks is unpleasant and irritating and often remains on the fabric after it enters the normal channels of commerce, where it causes further irritation to workers and users of such Water repellent fabrics. Moreover, they are not useful to impart water repellency to non-cellulose fibers such as nylon, Orlon, wool, etc.

It is one of the objects of my invention to produce a durable water repellent composition which does not depend upon the use of a quaternary ammonium coupling radical to affix a water repellent residue to a textile fiber and avoids the disadvantageous features arising from the use of a compound containing that radical.

Another object of my invention is to provide a durable water repellent composition and method of application which does not produce degradation products which must be removed from the cloth and which produces a substantially odor-free water repellent fabric and process.

Another object of my invention is to provide water repellent textile fibers and fabrics which Will at the same time have desirable spot resistance, crease proofing and loweredstatic electrical properties.

Another object of my invention is to provide water repellent compositions and methods of application of such compositions to textile fibers and fabrics which are equally applicable to a wide range of textile fibers and fabrics, such as .cotton, artificial silk and other synthetic fibers.

Another object of my invention is to provide aqueous emulsions of water repellent materials containing long Patented Dec. 4, 1962 ice chain fatty radicals which are stable under normal conditions of shipment and storage and which may be atfixed to textile fibers and fabrics by ordinary resin curing steps, to impart more durable water repellent characteristics to textiles than the water repellents now in use.

Various other objects and advantages of my invention will appear as this description proceeds.

The effectiveness of methylene distearamide as a water repellent on cotton cloth has hereto been experimentally tested. In that work the methylene distearamide was applied to the cotton fabric as a solution in glacial acetic acid. That work showed that, unlike stearamido-methylpyridinium chloride, the compound showed no tendency to chemically bond itself to the cellulose, and the water repellent finish produced by the deposited compound was insufficiently resistant to laundering to be of practical value.

A glacial acetic acid solution of the methylene distearamide was used in this experimental work for the application of the compound to the cotton fabric because the compound was found difficult, if not impossible, to suspend as a colloid, in an aqueous medium. I have invented a method by which I can secure a true colloidal dispersion of methylene distearamide and analagous com.- pounds of relatively high molecular weight in an efiicient and expeditious manner, which I have described and claimed in my copending application Serial No. 690,624, filed October 17, 1957, now US. Patent No. 2,972,548. That invention solved one of the major problems involved in the use of this class of compounds in rendering fibers and textiles Water repellent. By that invention an aqueous stable colloidal dispersion consisting of a continuous phase comprising a solution of about 1 part to about 5 parts per parts by weight of said colloidal dispersion of an acid-stable non-ionic surface active agent in water and a discontinuous phase comprising colloidal particles of a compound produced in situ having the formula (RCONH) CH in which R represents an aliphatic hydrocarbon chain containing 16 to 30 carbon atoms is obtained. By the present invention I provide a method for aifixing the long-chain methylene diamines to fibers and textile fabrics so as to impart water repellency which is retained through several washings or dry cleaning operations, and thereby provide an improved water repellent finish which is superior to those now commercially available.

In accordance with this invention, I prepare an aqueous colloidal dispersion which has at least two dispersed phases and a continuous aqueous phase which has at least one surface active agent dissolved therein. One of these dispersed phases consists of colloidally dispersed particles of a compound having the generic formula (RCONH CH in which R represents an aliphatic hydrocarbon chain of 16 to 30 carbon atoms, such as, for example, methylene distearamide (or methylene diotadecyl amide), methylene dioleyl amide, methylene dimontan amide, etc.

The second dispersed phase of this complex colloidal dispersion consists of colloidally dispersed particles or droplets of aurea-formaldehyde resin, a modified urea.- formaldehyde resin, a melamine-formaldehyde, a modified melamine formaldehyde or other resin which :is heatcuring and dispersible as a colloidal suspension or dispersion. The resin utilized should be of a composition such that, after it is cured, it contains no free or unreacted soluble or deliquescent material, such as free urea, glycol, glycerol or the like.

A modified urea-formaldehyderesinwhich I have found suitable for use in this composition is a reaction product of urea, formaldehyde and methanol which is in substantially the monomeric stage. A resin of this type is sold sea /n59 3 under the tradename of Rhonite R-Z. Another suitable resin is a methylated methylol melamine, such as Aerotex M-3 or Resloom M-75. Acetylene diureine formaldehyde resin is another suitable resin for my purpose. 7 When necessary to secure an expeditious cure of the particular heat-curing resin which forms the second dispersed phase of this complex dispersion, I include in the composition a catalyst which is adapted to hasten the curing of the particular resin involved. The catalyst used may be dissolved in the continuous aqueous phase of the composition or be emulsified as a third dispersed phase, depending upon its solubility in water. Citric acid and ammonium sulfate are suitable catalysts for expediting the heat-curing of a methylated methylol melamine resin. Zinc nitrate is a suitable catalyst for acetylene diureine formaldehyde resin. The amine hydrochloride catalysts, such as, for example, the hydrochloride of 2-amino-2- methyl-l-propanol (catalyst A-C) are suitable for use with a urea-formaldehyde paste and may be added to the composition in an amount within the range of about 0.25% to about 2.00% by weight, of the composition.

This complex colloidal dispersion may contain additional dispersed phases comprised of other water insoluble materials which are used in the treatment of textiles, such as, for example, parafiin wax, stearic acid and the like. I have found that the addition of a mineral oil to the composition is advantageous in that it appears both to aid in the emulsification of other ingredients and to suppress any tendency of the composition to foam during its application to a textile fiber or fabric.

I have also found that this complex colloidal dispersion may advantageously contain a film-forming polymer emulsion that imparts no rewetting action and that is fully compatible with the other components of the emulsion. Such a film-forming polymer appears to reduce the tendency of the resin fixed methylene diamides to flake or dust oif the fabric with use. Typical of such filmforming polymer emulsions that are compatible with the complex colloidal dispersion are polyvinyl acetate emulsion, polyacrylate emulsion, polystyrene emulsion and some synthetic rubber emulsions and latices.

In the preparation of this complex aqueous dispersion, I prepare a colloidal dispersion of a compound having the formula (RCONH) CH in which R represents an aliphatic hydrocarbon chain of 16 to 30 carbon atoms in an aqueous solution of a surface active agent. I may prepare this aqueous colloidal dispersion by the method described by my copending application Serial No. 690,624 referred to hereinbefore, although this invention is not limited to the preparation of the dispersion by that particular method or to the use of the particular colloidal dispersion claimed by that application.

The resin which forms the second dispersed phase of this complex aqueous dispersion may be dispersed directly in the aqueous dispersion of the (RCONH) CH compound. However, I prefer from a practical operating standpoint to prepare a second colloidal dispersion which carries the heat-curing resin as at least one of its dispersed phases and has a continuous phase comprising an aqueous solution of at least one surface active agent, and then mix this dispersion with the aqueous dispersion of the (RCONH) CH compound.

This second aqueous dispersion, carrying a heat-curing resin as a dispersed phase, may carry one or more textile treating materials, such as, stearic acid, paraffin wax, mineral oil, etc. as additional dispersed phases. This second dispersion may also carry the film-forming polymer emulsion as an additional dispersed phase. Alternatively, when it is desired to include such added textile treating materials in the final complex aqueous dispersion, they may be dispersed as discontinuous phases in one or more separate aqueous dispersions, and then these dispersions are mixed with the aqueous dispersion of the (RCONH) CH compound and of the heat-curing resin.

The first step of the method in accordance with this invention for rendering a textile fiber or fabric water repellent consists of wetting the fiber or fabric with a complex aqueous colloidal dispersion comprising a dispersed phase consisting of particles of a compound having the generic formula (RCONH) CH in which the R represents an aliphatic hydrocarbon chain of 16 to 30 carbon atoms, a second dispersed phase consisting of particles or droplets of a heat-curing resin, such as, for example, a ureaformaldehyde resin, a modified urea-formaldehyde resin, a melamine-formaldehyde resin, a modified melamineformaldehyde resin, mixtures of these resins, and the like with or without additional textile treating materials and a continuous phase comprising an aqueous solution of at least one surface active agent.

T he wet fiber or fabric is then dried. It may be permitted to dry at normal atmospheric temperature, but is preferably dried at an elevated temperature to speed up the operation. The elevated temperature used to dry the fiber or fabric may be, for example, a temperature within the range of about 212 F. to about 250 F. After the fiber or fabric is dried, it is subjected to an elevated tel. perature adapted to cure the particular heat-curing resin involved for a period of which will effect its complete cure. Thus, the curing temperature may be within the range of about 290 F. to about 330 F. for a period of time within the range of about 5 to about 10 minutes. After this curing operation, the fiber or fabric is permitted to cool to room temperature.

The method in accordance with this invention is applicable to awide range of textile fibers and fabrics, including cotton, viscose, cellulose acetate, and others. The treated fiber and fabric, in accordance with this invention, comprises individual fibers which carry a partial or complete coating of a compound of the generic formula (RCONH) CH in which R represents an aliphatic hydrocarbon chain of 16 to 30 carbon atoms which is bound to the fiber by a heat-cured synthetic resin. Treatment, in accordance with this invention, does not close the interstices of a fabric.

When the treatment includes a film-forming polymer emulsion it has been found that flaking or dusting of the resin from the fabric is better controlled and the treatment is more durable to both laundering and dry cleanmg.

I have been unable to determine the exact mechanism by which the heat-cured resin bonds the (RCONH) CH compound to the fiber. However, the fact remains that the result is a durable, water repellent finish which is re sistant to both laundering and dry cleaning. Thus, for example, a treated fabric, in accordance with this invention may have a spray rating of and retain this rating through several launderings, or dry cleanings. Furthermore, the fibers and fabrics will, at the same time, have desirable spot resistance, crease-proofing and lowered static electrical properties.

The following examples illustrate practical applications of my invention, but it will be understood that the invention is not limited to the examples chosen for the purposes of illustration.

EXAMPLE I Me'thylene Distearamide Emulsion Preparation A mixture of the following ingredients were mixed together and refluxed for a period of one hour at a temperature of 96-99 C.:

This mixture was then cooled to 76 C. and its pH ad- Parts by weight Sorbitan monopalmitate 1.5

Polyoxyethylene sorbitan monopalmitate 1.5 Water 14.7

This mixture was then vigorously stirred and homogenized to produce a uniform, stable dispersion in which methylene distearamide is the dispersed phase and an aqueous solution of sorbitan monopalmitate and polyoxyethylene sorbitan monopalmitate is the continuous phase.

Methylene Distearamia'e-Resin Emulsion The following ingredients were added to 15 parts by weight of the above-prepared methylene distearamide emulsion:

parts of modified urea-formaldehyde resin 1 part of monethanolamine hydrochloride as a catalyst and thoroughly admixed therewith. The resultant composition was then ready for use in the treatment of a textile fabric. The modified urea-formaldehyde resin used in this example consisted of a monomeric reaction product of urea, formaldehyde and methanol (Rhonite R2).

Fabric Treatment With Resin Emulsion Cotton corduroy was passed through a bath containing the above-prepared methylene distearamide-resin emulsion and thoroughly wet by the emulsion. The impregnated fabric was then dried and the resinous components carried thereon were cured at a temperature of 300 F. for 6 minutes.

The cotton corduroy treated in this manner for water repellency had an initial spray rating of 100. This rating remained unchanged through several launderings.

EXAMPLE II Methylene Distearamide Emulsion Preparation A mixture of the following ingredients were refluxed for A of an hour at a temperature of 195 F.-200 R:

Parts by weight Octadecylamide 20 Formaldehyde (37% solution) 8 Sorbitan monopalmitate 1 Water 55 After this period of reflux, 4.6 parts by weight of dipropylene glycol was added to the reaction mixture and its pH was adjusted to a value within the range of about 1 to about 4, preferably between 2.0 and 3.0 by the addition of approximately 0.5 part by weight of 20 Baum hydrochloric acid. The dipropylene glycol is added to keep the emulsion smooth; it also has foam suppressant properties. The resulting reaction mixture was then heated at 184188 F. for a period of one hour. The reaction mixture was then neutralized by the addition of approximately 0.4 part by weight of monoethanolamine, and then cooled, while stirring, to a temperature of 150 F.

H Methylene Distearamide-Resin Emulsion The following ingredients were then added to the resulting aqueous dispersion of methylene distearamide in an aqueous solution of sorbitan monopalmitate and dipropylene glycol:

Parts by weigh Modified urea formaldehyde resin 5.0 Mineral oil 2.0 Sorbitan monopalmitate 3.5

The additional emulsifier is added at this point to insure stability and freedom from flocculation. The resulting mixture was then stirred and permitted to cool until its temperature dropped to 1 0-0-105 F., and was then passed through a colloid mill. The resin emulsion is then ready for use in treatment of fabrics as was done in Example I.

The following optional treatment can be made to the above prepared resin emulsion to improve the wash fastness of the finished water repellent treatment. This optional modificaiton is best used for synthetic fibers and cloth containing synthetics; it may be omitted on cotton fabric and fibers as shown in Example I.

Optional Melamine Resin Treatment The following ingredients were then added to 8 parts by weight of the above resulting colloidal suspension:

Parts by weight Methylated methylol melamine resin 4 Citric acid 0.1

and thoroughly admixed therewith. The resulting composition was then ready for use in the treatment of a textile fiber or fabric.

Fabric Treatment With Resin Emulsion Cotton corduroy was passed through a bath of the composition prepared as described above, and thoroughly wet by the composition. The impregnated fabric was then dried and the resinous components carried thereby cured at a temperature of 320 F. for a period of 7 minutes.

The cotton corduroy treated in this manner was tested for water repellency and for the durability of the water repellent finish deposited thereon by this treatment. The treated fabric was found to have an initial spray rating of 100. This rating remained unchanged through three successive dry cleanings, and still retained a spray rating of after five successive washings, each conducted as pre scribed by the No. 3 wash test of the American Association of Textile Chemists and Colorists.

EXAMPLE III Wax Emulsion Preparation A wax emulsion having the following composition was prepared: Parts by weight Paraffin wax, 138 A.M.P. 20 Stearic acid 2 Sorbitan monopalmitate 3 Polyoxyethylene sorbitan monopalrnitate 3 Mineral oil 2 The above mixture was heated to. 225 F., whereupon it became clear. A mixture offour parts, by weight, of dipropylene glycol and 48 parts, by weight, of water, was heated to a temperature of 150 F. and added slowly to the foregoing mixture with good agitation. Eighteen parts of zirconyl acetate (13% Zn,O were :then added to the composition and uniformly admixed therewith. In place of zirconyl acetate, there can be used the equivalent amount of aluminum acetate (6% as powder). The composition was then passed through a colloid mill.

Wax-Resin Emulsion Fiftypartsby Weight of this wax emulsion as prepared abovewas then admixed with fifty parts by weight, of the methylene distearamide resin emulsion of Example-1L Fabric Treatment With Resin Emulsion A textile treating bath was prepared from the foregoing Wax-resin emulsion by adding the following ingredients to eight parts by weight of that composition:

Parts by Weight Urea-formaldehyde resin paste 20 Urea-formaldehyde polymer 3 Amine hydrochloride catalyst 1 These ingredients were uniformly admixed into the composition, and the bath was ready for use. The ureaformaldehyde polymer utilized in this example was a high molecular weight reaction product of urea and formaldehyde (Rhonite 414).

Fabric Treatment With Resin Emulsion A viscose-acetate gabardine was passed through a bath of the composition described above and thoroughly wet by the composition. The gabardine was then dried and the resin which it picked up was cured by heating the fabric at a temperature of 320 F. for a period of six to seven minutes.

The gabardine treated in this manner was then tested for water repellency and for the durability of the water repellent finish deposited therein by this treatment. The treated fabric was found to have an initial spray rating of 100 and the water repellent finish was found to have excellent resistance to dry cleaning.

EXAMPLE IV Methylene Distearamia'e Emulsion Preparation A mixture of the following ingredients were refluxed for A of an hour at a temperature of 195 F. to 200 F.

After this period of reflux, 5 parts by weight of dipropylene glycol was added to the reaction mixture and its pH was adjusted to a value within the range of about 1 to about 4, preferably between 2.0 and 3.0 by the addition of 20 Baum hydrochloric acid. The resulting reaction mixture was then heated at 184-l88 F. for a period of one hour. The reaction mixture was then neutralized by the addition of monoethanolamine, and then cooled, while stirring, to a temperature of 150 F. An aqueous solution having the following composition was then added to the reaction mixture:

. Parts by weight Sorbitan monopalmitate 3.5 Mineral oil 2.0 Water 5.5

This mixture was then passed through a colloid mill.

Methylene DisIearamide-Additive Emulsion In order to provide a product that would not dust oif or flake oif after application to the fabric, to 90 parts by weight of the above emulsion were added:

Parts by weight Wax emulsion (as prepared in Example III) 5 Polyvinylacetate emulsion 5 This composition was stirred until uniform.

Methylene Distearamide-Resin Emulsion The following ingredients were added to parts by weight of the above methylene distearamide-wax-polyvinyl-acetate emulsion:

and thoroughly admixed therewith. The resultant composition was then ready for use in the treatment of a textile fabric. The urea-formaldehyde resin paste is a commercial preparation containing about 5 0% resin and about 50% water, and is sold as Aerotex Cream 450.

Fabric Treatment With Resin Emulsion A cotton fabric was passed through a bath containing the above prepared methylene distearamide-resin emulsion and thoroughly wet by the emulsion. The impreg nated fabric was then dried and the resinous components carried thereon were cured as in the preceding examples.

The cotton fabric treated in this manner for water repellency had an initial spray rating of 100. The water repellent resin finish showed no dusting when flexed or subjected to a button-breaking operation.

It will be appreciated from the foregoing examples that the complex colloidal dispersions in accordance with this invention can be readily applied to textile fibers and fabrics and cured thereon to impart a durable Water repellency which is more resistant to laundering and dry cleaning than the Water repellents based on the use of long chain fatty radicals coupled with quaternary ammonium compounds, such as, stearamidomethylpyridinium chloride, which is widely used as the active ingredient in textile treating compositions of this type.

The heat-curing resin contained in these compositions, as already noted, bond the water repellent material, i.e., the (RCONHhCI-I compound, to the fibers to impart a durable water repellency to the fiber or fabric. In addition the cured resin imparts a crease-resistance to fabric which is an added advantage.

In carrying out the method of this invention there is no decomposition reaction which releases objectionable odors or leaves residues on the fiber. This is an important improvement over the compositions which utilize as an active ingredient a compound which contains a quaternary ammonium group. The widely used stearamidomethylpyridinium chloride decomposes with the release of objectionable odors and tends to leave an objectionable odoriferous residue on a textile fiber or fabric which are entirely avoided by my composition.

In the process of making the methylene distearamide emulsion, while I do not want to be bound by any theories regarding the reactions taking place, it is my belief that the chemical reaction involved here takes place in two steps. In the first step formaldehyde is believed to react with the long chain aliphatic amide to form a methylol derivative according to the following equation.

RCONH +CH O+ RCONHCH OH In the second step, this methylol derivative is believed to react, when under acid conditions, with an additional quantity of aliphatic amide to form the diamide, according to the following equation:

RCONHCH OH+RCONH (RCONH) CH +H O Thus, according to these theories, the product of the reaction of octadecyl amide (stearyl amide) with formaldehyde results in a product which has the following structural formula:

This compound is alternatively known as methylene distearamide or as distearamide methane.

While I have specifically exemplified the compositions, the method for their application and the water repellent fibers and fabrics, in accordance with my invention, it will be understood that these are for illustrative purposes only and that various modifications and changes may be made in the various formulas and in the method for their preparation and application, without departing from the spirit of my invention or the scope of the following claims:

-I claim:

1. A substantially organic solvent-free aqueous colloidal dispersion having a continuous phase comprising a solution of an acid-stable, non-ionic surface active agent selected from the group consisting of polyoxyethylene sorbi tan monopalmitate and sorbitan monopalmitate in Water, a discontinuous phase comprising colloidal particles of a compound produced in situ having the formula (RCONH) CH in which R represents an aliphatic hydrocarbon chain containing 16 to 30 carbon atoms and a second discontinuous phase comprising a heat-curable compound selected from the group consisting of methylol urea, methanol modified methylol urea, methylol melamine, and methylated methylol melamine.

2. A substantially organic solvent-free aqueous colloidal dispersion having a continuous phase comprising a solution of an acid-stable, non-ionic surface active agent selected from the group consisting of polyoxyethylene sorbitan monopalmitate and sorbitan monopalmitate in Water, a discontinuous phase comprising colloidal particles of a compound produced in situ having the formula (RCONPD CH in Which R represents an aliphatic hydrocarbon chain containing 16 to 30 carbon atoms and a second discontinuous phase comprising a heat-curable compound selected from the group consisting of methylol urea, methanol modified methylol urea, methylol melamine, and methylated methylol melamine, and a third discontinuous phase comprising a film-forming polymer selected from the group consisting of polyvinylacetate and polystyrene.

3. A substantially organic solvent-free aqueous colloidal dispersion having a continuous phase comprising a solution of an acid-stable, non-ionic surface active agent selected from the group consisting of polyoxyethylene sorbitan monopalmitate and sorbitan monopalmitate in water, a discontinuous phase comprising colloidal particles of a compound produced in situ having the formula (RCONH) CH in Which R represents an aliphatic hydrocarbon chain containing 16 to 30 carbon atoms, a second discontinuous phase comprising a heatcurable compound selected from the group consisting of methylol urea, methanol modified methylol urea, methylol melamine and methylated methylol melamine, a third discontinuous phase comprising mineral oil, and a catalyst adapted to hasten the curing of the heat-curable compound.

4. A substantially organic solvent-free aqueous colloidal dispersion having a continuous phase comprising a solution of an acid-stable, non-ionic surface active agent selected from the group consisting of polyoxyethylene sorbitan monopalmitate and sorbitan monopalmitate in water, a discontinuous phase comprising colloidal particles of a compound produced in situ having the formula (RCONH) CH in Which R represents an aliphatic hydrocarbon chain containing 16 to 30 carbon atoms, a second discontinuous phase comprising heat-curable methanol modified methylol urea, and a catalyst adapted to hasten the curing of said methylol urea.

5. A substantially organic solvent-free aqueous colloidal dispersion having a continuous phase comprising a solution of an acid-stable, non-ionic surface active agent selected from the group consisting of polyoxyethylene sorbitan monopalmitate and sorbitan monopalmitate in Water, a discontinuous phase comprising colloidal particles of a compound produced in situ having the formula (RCONH) CH in which R represents an aliphatic hydrocarbon chain containing 16 to 30 carbon atoms, a second discontinuous phase comprising heat-curable methylol urea and a catalyst adapted to hasten the curing of the said methylol urea and a third discontinuous phase comprising film-forming polyvinylacetate.

6. A substantially organic solvent-free aqueous colloidal dispersion having a continuous phase comprising a solution of an acid-stable, non-ionic surface activeagent selected from the group consisting of polyoxyethylene sorbitan monopalmitate and sorbitan monopalmitate in water, a discontinuous phase comprising colloidal particles of a compound produced in situ having the formula (RCONH) CH in which R represents an aliphatic hydrocarbon chain containing 16 to 30 carbon atoms, a second discontinuous phase comprising heat-curable methylated methylol melamine and a catalyst adapted to hasten the curing of the said methylol melamine.

7. A substantially aqueous colloidal dispersion consisting of a continuous phase of a solution of an acidstable, non-ionic surface active agent selected from the group consisting of polyoxyethylene sorbitan monopalmitate and sorbitan monopalmitate in Water, a discontinuous phase consisting of colloidal particles of methylene distearamide produced in situ, a second discontinuous phase consisting of a heat-curable compound selected from the group consisting of methoylol urea, methanol modified methylol urea, methylol melamine and methylated methylol melamine, and a catalyst adapted to hasten the curing of the said heat-curable compound, and a third discontinuous phase consisting of a filrn-forming polymer selected from the group consisting of polyvinyl acetate and polystyrene.

8. A substantially aqueous colloidal dispersion consisting of a continuous phase of a solution of polyoxyethylene sorbitan monopalmitate and sorbitan monopalmitate in water, a discontinuous phase consisting of colloidal particles of methylene distearamide produced in situ, a second discontinuous phase consisting of heatcurable methanol modified methylol urea, and a catalyst adapted to hasten the curing of the said methylol urea.

9. A substantially aqueous colloidal dispersion consisting of a continuous phase of a solution of sorbitan monopalmitate in water, a discontinuous phase consisting of colloidal particles of methylene distearamide produced in situ, a second discontinuous phase consisting of heat-curable methylol urea, and a catalyst adapted to hasten the curing of the said methylol urea, and a third discontinuous phase consisting of film-forming polyvinylacetate.

10. A substantially aqueous colloidal dispersion consisting of a continuous phase of a solution of an acidstable nonionic surface active agent selected from the group consisting of polyoxyethylene sorbitan monopalmitate and sorbitan monopalmitate in water, a discontinuous phase consisting of colloidal particles of methylene distearamide produced in situ, a second discontinuous phase consisting of heat-curable methylated methylol melamine, and a catalyst adapted to hasten the curing of said methylol melamine.

References Cited in the file of this patent UNITED STATES PATENTS 2,423,428 Pollard July 1, 1947 2,491,249 Cathers et a1 Dec. 13, 1949 2,505,649 Pikl Apr. 25, 1950 2,511,113 La Piana et a1 June 13, 1950 2,861,054 Rust et al. Nov. 18, 1958 2,981,704 Herbes et al. Apr. 25, 1961 OTHER REFERENCES Schwartz et al.: Surface Active Agents and Detergents, volume II (1958), Interscience Pub. Inc., New York, page 134. 

1. A SUBSTANTIALLY ORGANIC SOLVENT-FREE AQUEOUS COLLOIDA DISPERSION HAVING A CONTINUOUS PHASE COMPRISING A SOLUTION OF AN ACID-STABLE, NON-IONIC SURFACE ACTIVE AGENT SELECTED FROM THE GROUP CONSISTING OF POLYOXETHYLENE SORBITAN MONOPALMITATE AND SORBITAN MONOPALMITATE IN WATER, A DISCONTINOUS PHASE COMPRISING COLLOIDAL PARTICLES OF A COMPOUND PRODUCED IN SITU HAVING THE FORMULA (RCONH)2CH2 IN WHICH R REPRESENTS AN ALIPHATIC HYDROCARBON CHAIN CONTINING 16 TO 30 CARBON ATOMS AND A SECOND DISCONTINUOUS PHASE COMPRISING A HEAT-CURABLE COMPOUND SELECTED FROM THE GROUP CONSISTING OF METHYLOL UREA, METHANOL MODIFIED METHYLOL UREA, METHYLOL MELAMINE, AND METHYLATED METHYLOL MELAMINE. 